JP2010500709A - Cell or battery having metallic lithium electrode and electrolyte therefor - Google Patents
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Abstract
リチウムまたはリチウム含有合金で作られた負極（アノード）を備える充電池用の電解質であって、１種類または数種類の非水性有機溶媒と、１種類または数種類のリチウム塩と、リチウム電極のサイクル寿命を増加させる１種類または数種類の添加剤とを含む電解質。ここで電解質の添加剤は式Ｌｉ２Ｓｎを有する多硫化リチウムである。このような電解質と、リチウムまたはリチウム含有合金で作られた負極と、金属リチウムまたは第２のリチウム含有合金で作られた負極とを含む電池。電解質の溶液は、テトラヒドロフラン、２−メチルテトラヒドロフラン、ジメチルカーボネート、ジエチルカーボネート エチルメチルカーボネート、メチルプロピルカーボネート、メチルプロピルプロピオネート、エチルプロピルプロピオネート、メチルアセテート、エチルアセテート、プロピルアセテート、ジメトキシエタン １，３−ジオキサラン、ジグライム（２−メトキシエチルエーテル）、テトラグライム、エチレンカーボネート プロピレンカーボネート、γ−ブチロラクトン、およびスルホランを含む群より選択される少なくとも１種類の溶媒または数種類の溶媒を含むことができる。電解質の溶液は、ヘキサフルオロリン酸リチウム（ＬｉＰＦ６）、ヘキサフルオロヒ酸リチウム（ＬｉＡｓＦ６）、過塩素酸リチウム（ＬｉＣＩＯ４）、リチウムスルホニルイミドトリフルオロメタン（ＬｉＮ（ＣＦ３ＳＯ２）２））、およびトリフルオロスルホン酸リチウム（ＣＦ３ＳＯ３Ｌｉ）、もしくはその他のリチウム塩、もしくは別のアルカリ金属の塩、またはそれらの混合物からなる群より選択される少なくとも１種類の塩または数種類の塩をさらに含むことができる。An electrolyte for a rechargeable battery comprising a negative electrode (anode) made of lithium or a lithium-containing alloy, and having a cycle life of one or several non-aqueous organic solvents, one or several lithium salts, and a lithium electrode An electrolyte comprising one or several additives to increase. Wherein the electrolyte additives are lithium polysulphide having the formula Li 2 S n. A battery comprising such an electrolyte, a negative electrode made of lithium or a lithium-containing alloy, and a negative electrode made of metallic lithium or a second lithium-containing alloy. The electrolyte solution is tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, methyl propyl propionate, ethyl propyl propionate, methyl acetate, ethyl acetate, propyl acetate, dimethoxyethane 1, It can contain at least one solvent selected from the group comprising 3-dioxalane, diglyme (2-methoxyethyl ether), tetraglyme, ethylene carbonate propylene carbonate, γ-butyrolactone, and sulfolane, or several solvents. The electrolyte solution was lithium hexafluorophosphate (LiPF 6 ), lithium hexafluoroarsenate (LiAsF 6 ), lithium perchlorate (LiCIO 4 ), lithium sulfonylimide trifluoromethane (LiN (CF 3 SO 2 ) 2 )) And at least one salt or several salts selected from the group consisting of lithium trifluorosulfonate (CF 3 SO 3 Li), or other lithium salts, or other alkali metal salts, or mixtures thereof Further can be included.
Description
本発明は、電気化学的電力工学に関し、特に、金属リチウムまたはリチウム含有合金で作られた負極（アノード）を含む電気エネルギーの二次的化学的供給源（充電池）に関する。本発明は、特定の電解質によってリチウム電極のサイクル寿命を増加する方法にも関する。 The present invention relates to electrochemical power engineering, and more particularly to a secondary chemical source (rechargeable battery) of electrical energy including a negative electrode (anode) made of metallic lithium or a lithium-containing alloy. The present invention also relates to a method for increasing the cycle life of a lithium electrode with a specific electrolyte.
金属リチウムは、高い比容量（３．８８Ａｈ／ｇ）を有するので、高容量充電池の負極の形成のための最も魅力的な材料の１つとなっている。 Metallic lithium has one of the most attractive materials for forming negative electrodes for high capacity rechargeable batteries because of its high specific capacity (3.88 Ah / g).
リチウム金属電極の欠点の１つとしてサイクル寿命の短さが知られており、これはリチウムがカソード析出中にデンドライトを形成しやすいことによって引き起こされる。 One shortcoming of lithium metal electrodes is known to be short cycle life, which is caused by the tendency of lithium to form dendrites during cathode deposition.
金属リチウムおよび非水性電解質に基づく電気化学系は、熱力学的に安定ではないことが知られている。例えば、電解質成分とのリチウムの相互作用の生成物の皮膜がリチウム電極表面上に常に形成される。この皮膜の性質は、電解質系の成分の化学的性質によって決定される。リチウム電極の表面上の不動態皮膜は、多くの電解質中で形成されることがあり、リチウムイオンに対する高いイオン伝導性と、電解質自体に対する良好な保護特性とを有する。場合によっては、このような皮膜は「固体電解質界面」と呼ばれる。これらは、リチウムイオンに対する高い伝導性、および低い電子伝導性を有するため、これらは、続いて起こる電解質成分との相互作用から金属リチウムを保護し、同時に電気化学反応の進行を妨害しない。カソードの分極中、一部のリチウムは、不動態層の下のアノード上にめっきされる。このようにめっきされたリチウムからは、アノードの大部分に十分に結合した緻密な析出物が形成される（「コンパクトリチウム（ｃｏｍｐａｃｔ ｌｉｔｈｉｕｍ）」）。さらにリチウムは、欠陥または不純物を含有する不動態皮膜領域中にデンドライトの形態で析出する（「デンドライトリチウム」）。緻密リチウムおよびデンドライトリチウムと電解質系の成分との相互作用中、一部のリチウムは、熱力学的に安定でほぼ不溶性の化合物（酸化物およびフッ化物）を形成する（「化学結合リチウム」）。緻密リチウム、デンドライトリチウム、および化学結合リチウムの間のバランスは、電極表面の状態によって、電解質系の組成および性質によって、分極の形態によって、およびカソード析出中にリチウムがめっきされるアノードの基材の性質によって決定される。最終的に、リチウムサイクルの効率を決定するのはこのバランスである。 It is known that electrochemical systems based on metallic lithium and non-aqueous electrolytes are not thermodynamically stable. For example, a film of a product of lithium interaction with the electrolyte component is always formed on the lithium electrode surface. The nature of the coating is determined by the chemical nature of the electrolyte system components. The passive film on the surface of the lithium electrode may be formed in many electrolytes and has high ionic conductivity for lithium ions and good protective properties for the electrolyte itself. In some cases, such a coating is referred to as a “solid electrolyte interface”. Since they have high conductivity to lithium ions and low electronic conductivity, they protect metallic lithium from subsequent interaction with the electrolyte components and at the same time do not interfere with the progress of the electrochemical reaction. During cathode polarization, some lithium is plated on the anode under the passive layer. The lithium thus plated forms a dense precipitate that is well bonded to the bulk of the anode ("compact lithium"). Furthermore, lithium precipitates in the form of dendrites in the passive film region containing defects or impurities (“dendritic lithium”). During the interaction of dense lithium and dendritic lithium with the components of the electrolyte system, some lithium forms thermodynamically stable and nearly insoluble compounds (oxides and fluorides) ("chemically bonded lithium"). The balance between dense lithium, dendritic lithium, and chemically bonded lithium depends on the state of the electrode surface, on the composition and nature of the electrolyte system, on the form of polarization, and on the anode substrate on which the lithium is plated during cathode deposition. Determined by nature. It is this balance that ultimately determines the efficiency of the lithium cycle.
アノードの分極中、緻密リチウムは溶解し、基材との電子接触が良好な領域中でデンドライトリチウムは部分的に溶解する。デンドライトリチウムの非溶解部分は、微細分散した粉末を形成し、これはリチウム電極の表面上に蓄積する。 During the anode polarization, the dense lithium dissolves and the dendrite lithium partially dissolves in the region where the electronic contact with the substrate is good. The undissolved portion of dendritic lithium forms a finely dispersed powder that accumulates on the surface of the lithium electrode.
リチウム金属のサイクル寿命を増加する方法を本発明において提案する。本発明では、多硫化リチウムを電解質系中に加え、リチウムデンドライトの形成速度が、電解質中に溶解した多硫化リチウムとの相互作用によって起こるリチウム溶解の速度以下となる条件下で充電（リチウムのアノード析出）を行うことを提案する。 A method for increasing the cycle life of lithium metal is proposed in the present invention. In the present invention, lithium polysulfide is added to the electrolyte system, and charging is performed under the condition that the formation rate of lithium dendrite is less than the rate of lithium dissolution caused by the interaction with lithium polysulfide dissolved in the electrolyte (lithium anode). We propose to perform precipitation).
本発明の第１の態様によると、リチウムまたはリチウム含有合金で作られた負極（アノード）を備える充電池用の電解質であって、１種類または数種類の非水性有機溶媒と、１種類または数種類のリチウム塩と、リチウム電極のサイクル寿命を増加する１種類または数種類の添加剤とを含む電解質が提供される。 According to a first aspect of the present invention, an electrolyte for a rechargeable battery comprising a negative electrode (anode) made of lithium or a lithium-containing alloy, comprising one or several non-aqueous organic solvents and one or several An electrolyte is provided that includes a lithium salt and one or more additives that increase the cycle life of the lithium electrode.
電解質の溶液は、好ましくは、テトラヒドロフラン、２−メチルテトラヒドロフラン、ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネート、メチルプロピルカーボネート、メチルプロピルプロピオネート、エチルプロピルプロピオネート、メチルアセテート、エチルアセテート、プロピルアセテート、ジメトキシエタン、１，３−ジオキサラン、ジグライム（２−メトキシエチルエーテル）、テトラグライム、エチレンカーボネート、プロピレンカーボネート、γ−ブチロラクトン、およびスルホランを含む群より選択される少なくとも１種類の溶媒または数種類の溶媒を含む。 The electrolyte solution is preferably tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, methyl propyl propionate, ethyl propyl propionate, methyl acetate, ethyl acetate, propyl acetate, At least one solvent or several solvents selected from the group comprising dimethoxyethane, 1,3-dioxalane, diglyme (2-methoxyethyl ether), tetraglyme, ethylene carbonate, propylene carbonate, γ-butyrolactone, and sulfolane Including.
電解質の溶液は、好ましくは、ヘキサフルオロリン酸リチウム（ＬｉＰＦ６）、ヘキサフルオロヒ酸リチウム（ＬｉＡｓＦ６）、過塩素酸リチウム（ＬｉＣｌＯ４）、リチウムスルホニルイミドトリフルオロメタン（ＬｉＮ（ＣＦ３ＳＯ２）２）、トリフルオロスルホン酸リチウム（ＣＦ３ＳＯ３Ｌｉ）、もしくは別のリチウム塩、もしくは別のアルカリ金属塩、またはそれらの混合物からなる群より選択される少なくとも１種類の塩または数種類の塩を含む。 The electrolyte solution is preferably lithium hexafluorophosphate (LiPF 6 ), lithium hexafluoroarsenate (LiAsF 6 ), lithium perchlorate (LiClO 4 ), lithium sulfonylimide trifluoromethane (LiN (CF 3 SO 2 ) 2 ) at least one salt selected from the group consisting of lithium trifluorosulfonate (CF 3 SO 3 Li), or another lithium salt, or another alkali metal salt, or a mixture thereof; Including.
電解質の添加剤は好都合には、式Ｌｉ２Ｓｎを有する多硫化リチウムである。 Additives electrolyte conveniently in the lithium polysulphide having the formula Li 2 S n.
多硫化リチウムにおけるｎの値は好ましくは、端点の値を含めて２〜２０の範囲内、または端点の値を含めて２〜１２の範囲内、または端点の値を含めて１２〜２０の範囲内である。 The value of n in lithium polysulfide is preferably in the range of 2 to 20 including the end point value, or in the range of 2 to 12 including the end point value, or in the range of 12 to 20 including the end point value. Is within.
好ましい実施形態においては、リチウム塩の濃度は、非プロトン性溶媒（溶媒混合物）中における使用される塩の飽和溶液濃度の０．１〜９０％の範囲内にある。 In a preferred embodiment, the concentration of the lithium salt is in the range of 0.1 to 90% of the saturated solution concentration of the salt used in the aprotic solvent (solvent mixture).
好ましい実施形態においては、多硫化リチウム濃度は、０．０１Ｍから、非プロトン性溶媒（溶媒混合物）中における使用される塩の飽和溶液濃度の９０％までである。 In a preferred embodiment, the lithium polysulfide concentration is from 0.01 M to 90% of the saturated solution concentration of the salt used in the aprotic solvent (solvent mixture).
塩の飽和濃度は、使用される個別の塩／溶媒系に依存し、温度および圧力にも依存することは理解されたい。しかし、一般的な動作条件における飽和濃度と比較した塩または多硫化リチウムの濃度が重要であり、このことが、上限濃度を規定するために％値での相対濃度が使用される理由である。多硫化物濃度の下限に関しては、少なくとも０．０１Ｍの最小絶対濃度が好ましい。 It should be understood that the saturation concentration of salt depends on the particular salt / solvent system used and also on temperature and pressure. However, the concentration of salt or lithium polysulfide compared to the saturation concentration in general operating conditions is important, which is why the relative concentration in% values is used to define the upper concentration limit. For the lower limit of the polysulfide concentration, a minimum absolute concentration of at least 0.01M is preferred.
本発明の第２の態様によると、金属リチウムまたは第１のリチウム含有合金で作られた負極（アノード）と、第１の態様による電解質とを含む電気化学セルまたは電池が提供される。 According to a second aspect of the present invention there is provided an electrochemical cell or battery comprising a negative electrode (anode) made of metallic lithium or a first lithium-containing alloy and an electrolyte according to the first aspect.
セルまたは電池は、好ましくは、金属リチウム、または第１のリチウム含有合金とは異なる第２のリチウム合金、もしくは第１のリチウム含有合金と同じ第２のリチウム含有合金で作られた正極（カソード）を含む。 The cell or battery is preferably a positive electrode (cathode) made of metallic lithium, or a second lithium alloy different from the first lithium-containing alloy, or the same second lithium-containing alloy as the first lithium-containing alloy. including.
本発明のある実施形態は、標準温度および圧力、すなわち２５℃および１ａｔｍにおける動作に適合している。 Certain embodiments of the invention are adapted for operation at standard temperature and pressure, ie, 25 ° C. and 1 atm.
別の実施形態は、−４０〜＋１５０℃、−２０〜＋１１０℃、または−１０〜＋５０℃の範囲の温度での動作に適合させることができる。他の温度および圧力ならびにそれらの範囲も有用となり得る。 Another embodiment can be adapted for operation at temperatures in the range of -40 to + 150 ° C, -20 to + 110 ° C, or -10 to + 50 ° C. Other temperatures and pressures and ranges can also be useful.
本発明がより十分に理解されるため、および実行可能な方法を示すために、これより例として以下の図面を参照する。 In order that this invention be more fully understood and to illustrate a feasible method, reference is now made to the following drawings by way of example.
リチウム電極のサイクル寿命を改善する問題を解決するためにいくつかの方法を使用することができる。 Several methods can be used to solve the problem of improving the cycle life of the lithium electrode.
第１の方法は、リチウム電極の表面上に硬い電解質皮膜（有機または非有機）を形成することに基づいている。このような皮膜は多数の必要な性質、
・ 高いリチウムイオン伝導性
・ 高いリチウムイオン輸率
・ 低い電子伝導性
・ 良好な機械的性質（強度および弾性）
・ 金属リチウム表面への高い付着性
を有する。
The first method is based on forming a hard electrolyte film (organic or non-organic) on the surface of the lithium electrode. Such a film has many necessary properties,
・ High lithium ion conductivity ・ High lithium ion transport number ・ Low electronic conductivity ・ Good mechanical properties (strength and elasticity)
-High adhesion to lithium metal surface.
固体電解質の皮膜は、金属リチウムと電解質成分との接触中に形成することができ、および／またはリチウム電極製造プロセス中に特別に形成することもできる（例えば、気相からのモノマーの重合によって、またはケイ素などの種々の物質の真空蒸着によって形成できる）。この方法の主要な欠点は、このような保護皮膜の性質がリチウム電極のサイクル寿命中に徐々に低下することである。 The solid electrolyte coating can be formed during the contact between the lithium metal and the electrolyte component, and / or can be specially formed during the lithium electrode manufacturing process (eg, by polymerization of monomers from the gas phase, Or by vacuum deposition of various materials such as silicon). The main drawback of this method is that the properties of such protective coatings gradually deteriorate during the cycle life of the lithium electrode.
第２の方法は、電解質中に特定の成分を加えることを含む。可能性のあるすべての添加剤は、作用機構により大まかに２つの大きなグループに分けることができる。 The second method involves adding certain components in the electrolyte. All possible additives can be roughly divided into two large groups depending on the mechanism of action.
１．界面活性剤。これらは、溶液からリチウム電極表面上に吸着されて保護皮膜（層）を形成する。このような種類の添加剤は、電解質系の成分との相互作用からリチウム電極表面を保護する一方、吸着した層を通過するリチウムイオンの移動は妨害せず、電気化学反応の進行も妨害しない。多くの種類の界面活性化合物（アルコールなど）を添加剤として使用することができる。 1. Surfactant. These are adsorbed from the solution onto the surface of the lithium electrode to form a protective film (layer). Such types of additives protect the lithium electrode surface from interaction with the components of the electrolyte system, but do not hinder the movement of lithium ions through the adsorbed layer and do not hinder the progress of the electrochemical reaction. Many types of surface active compounds (such as alcohols) can be used as additives.
２．化学的活性（反応性）添加剤。以下のように区別することができる。
・ 金属リチウムとの相互作用の間にリチウム表面上に高イオン伝導性の保護皮膜を形成する添加剤。このような添加剤の中では、リチウムのカソード分極またはアノード分極の間に生成されるイオンまたはフリーラジカルによって重合を開始することができる種々のビニルモノマーが挙げられる。
2. Chemically active (reactive) additive. A distinction can be made as follows.
-An additive that forms a protective film with high ion conductivity on the lithium surface during the interaction with metallic lithium. Among such additives are various vinyl monomers that can be polymerized by ions or free radicals generated during cathodic or anodic polarization of lithium.
・ 合金を形成する添加剤。これらは、電解質に対して可溶性であり、リチウム析出物の電位よりも高い正電位でカソード分極プロセス中にアノード上に析出することによって金属リチウムと合金を生成することができる金属化合物である。カルシウム、マグネシウム、およびアルミニウムのハロゲン化合物（ハロゲン化物）をこのような種類の化合物と見なすことができる。 -Additives that form alloys. These are metallic compounds that are soluble in the electrolyte and can form alloys with metallic lithium by depositing on the anode during the cathodic polarization process at a positive potential higher than that of the lithium precipitate. Calcium, magnesium, and aluminum halides (halides) can be considered as this type of compound.
・ アノード分極中に正極において還元可能な可溶性化合物を、（金属リチウムと反応した場合に）生成する酸化−還元添加剤。これらは、いわゆるデンドライト「捕捉剤」または金属リチウムの「溶媒」となる。 An oxidation-reduction additive that, when reacted with metallic lithium, produces soluble compounds that can be reduced at the positive electrode during anodic polarization. These serve as so-called dendrite “scavengers” or “solvents” for metallic lithium.
デンドライト「捕捉剤」の使用は、リチウム電極のサイクル寿命の改善のために最も有効な方法の１つである。デンドライト「捕捉剤」は、多数の特定の性質を有するべきである。 The use of dendrite “scavengers” is one of the most effective methods for improving the cycle life of lithium electrodes. A dendrite “scavenger” should have a number of specific properties.
その酸化された形態は、
・ 電解質に対して十分可溶性であり、
・ 金属リチウムに対して高い反応性があり、
・ リチウム表面上の不動態皮膜を容易に透過し、
・ 電解質系の他の成分に対して不活性であるべきである。
Its oxidized form is
Is sufficiently soluble in electrolytes,
・ High reactivity to lithium metal,
Easily penetrates the passive film on the lithium surface,
• Should be inert to other components of the electrolyte system.
その還元された形態は、
・ リチウム表面上に保護皮膜が形成されるように、電解質に対する溶解性はわずかであり、
・ 高リチウムイオン伝導性および低電子伝導性を有する還元生成物の不動態皮膜を形成し、
・ 正極減極剤の酸化電位と同じまたは同様の範囲の電位において正極上で容易に酸化されるが、同時に正極を不動態化させることはなく、
・ 正極減極剤に対して不活性となるべきである。
Its reduced form is
・ Solubility to electrolyte is slight so that a protective film is formed on the lithium surface,
・ Form a passive film of reduction product with high lithium ion conductivity and low electron conductivity,
It is easily oxidized on the positive electrode at a potential in the same or similar range as the oxidation potential of the positive electrode depolarizer, but does not passivate the positive electrode at the same time,
• Should be inert to the positive electrode depolarizer.
硫黄および多硫化リチウムは、このようなデンドライト「捕捉剤」となることができる。実際、硫化物系において、金属リチウムは硫黄（硫黄が電解質中に溶解されている場合）または多硫化リチウムのいずれかと反応する。
２Ｌｉ＋Ｓ８→Ｌｉ２Ｓ８
２Ｌｉ＋Ｌｉ２Ｓｎ→Ｌｉ２Ｓｎ−１＋Ｌｉ２Ｓ↓
Sulfur and lithium polysulfide can be such dendrites “scavengers”. In fact, in sulfide systems, metallic lithium reacts with either sulfur (if sulfur is dissolved in the electrolyte) or lithium polysulfide.
2Li + S 8 → Li 2 S 8
2Li + Li 2 S n → Li 2 S n-1 + Li 2 S ↓
硬い可溶性生成物である硫化リチウムの皮膜がこのプロセスでリチウム表面に形成される。この皮膜はリチウム電極上の電気化学的プロセスの進行を妨害しない。 A film of lithium sulfide, a hard soluble product, is formed on the lithium surface in this process. This coating does not interfere with the progress of the electrochemical process on the lithium electrode.
硫化リチウムは、硫黄を生成し、十分に可溶性の化合物である多硫化リチウムと反応することができる。多硫化リチウムは以下の反応によって液相中で形成される。
Ｌｉ２Ｓ＋ｎＳ→Ｌｉ２Ｓｎ＋１
Lithium sulfide produces sulfur and can react with lithium polysulfide, a sufficiently soluble compound. Lithium polysulfide is formed in the liquid phase by the following reaction.
Li 2 S + nS → Li 2 S n + 1
多硫化リチウムの溶解性は、電子供与体−受容体の性質、および使用される溶媒の極性に大きく依存し、さらに多硫化物鎖の長さにも依存しており、多硫化物鎖の長さは溶媒および電解質塩の性質および濃度に依存する。 The solubility of lithium polysulfide is highly dependent on the nature of the electron donor-acceptor and the polarity of the solvent used, and also on the length of the polysulfide chain. The length depends on the nature and concentration of the solvent and electrolyte salt.
デンドライト「捕捉剤」としての多硫化リチウムは、他の添加剤と比較した場合に多数の利点を有している。すなわち、これらはより低い当量を有し、良好な溶解性を有して長鎖および中鎖の多硫化物を形成し、短鎖多硫化物の形態ではより低い溶解性を有する。
［実施例］
Lithium polysulfide as a dendrite “scavenger” has a number of advantages when compared to other additives. That is, they have a lower equivalent weight, have good solubility to form long and medium chain polysulfides, and have lower solubility in the form of short chain polysulfides.
[Example]
２つのリチウム電極と、それらの電極の間に配置したセパレータのＣｅｌｇａｒｄ ３５０１（日本国、東京の東燃化学株式会社の商標であり、ニューヨーク州ピッツフォードのＭｏｂｉｌ Ｃｈｅｍｉｃａｌ Ｃｏｍｐａｎｙ，Ｆｉｌｍｓ Ｄｉｖｉｓｉｏｎよりも入手可能）とを使用してセルを作製した。このセパレータ膜はセルに挿入する前に電解質を吸収させた。リチウム電極は、厚さ３８ミクロンの高純度リチウム箔（米国のＣｈｅｍｅｔａｌｌ Ｆｏｏｔｅ Ｃｏｒｐｏｒａｔｉｏｎより入手可能）から作製した。リチウム電極の電流コレクタとして銅箔を使用した。スルホラン（９９．８％、英国のＳｉｇｍａ−Ａｌｄｒｉｃｈより入手可能なＧＣ用標準物質）中のトリフルオロメタンスルホン酸リチウム（ミネソタ州セントポールの３Ｍ Ｃｏｒｐｏｒａｔｉｏｎより入手可能）の１Ｍ溶液を電解質として使用した。 Celgard 3501 (a trademark of Tonen Chemical Co., Ltd., Tokyo, Japan; available from Mobile Chemical Company, Films Division, Pittsford, NY) with two lithium electrodes and a separator placed between them A cell was fabricated using This separator membrane absorbed the electrolyte before being inserted into the cell. The lithium electrode was made from a high purity lithium foil of 38 microns thickness (available from Chemetall Foot Corporation, USA). Copper foil was used as the current collector for the lithium electrode. A 1M solution of lithium trifluoromethanesulfonate (available from 3M Corporation, St. Paul, Minn.) In sulfolane (99.8%, a GC reference material available from Sigma-Aldrich, UK) was used as the electrolyte.
電池テスターのバイトロード（Ｂｉｔｒｏｄｅ）ＭＣＶ １６−０．１−５（Ｂｉｔｒｏｄｅ Ｃｏｒｐｏｒａｔｉｏｎ）上で０．２ｍＡ／ｃｍ２の電流負荷で上記セルのサイクル試験を行った。カソードおよびアノードの分極はそれぞれ１時間行った。このセルのサイクル中に得られたクロノポテンショグラムを図１に示す。 The cell was cycle tested with a current load of 0.2 mA / cm 2 on a battery tester Vitrode MCV 16-0.1-5 (Vitrode Corporation). The cathode and anode were each polarized for 1 hour. The chronopotentiogram obtained during this cell cycle is shown in FIG.
（多硫化リチウムを含有する電解質の調製）
２ｇの昇華させた９９．５％硫黄（英国のフィッシャー・サイエンティフィック）および０．５７ｇの９８％硫化リチウム（英国のＳｉｇｍａ−Ａｌｄｒｉｃｈ）を、共に高速ミル（Ｍｉｃｒｏｔｒｏｎ ＭＢ５５０）中で１５〜２０分間、乾燥アルゴン雰囲気（含水率２０〜２５ｐｐｍ）下で粉砕した。硫化リチウムおよび硫黄の粉砕混合物をフラスコに入れ、５０ｍｌの電解質をそのフラスコに加えた。スルホラン（９９．８％、英国のＳｉｇｍａ−Ａｌｄｒｉｃｈより入手可能なＧＣ用標準物質）中のトリフルオロメタンスルホン酸リチウム（ミネソタ州セントポールの３Ｍ Ｃｏｒｐｏｒａｔｉｏｎより入手可能）の１Ｍ溶液を電解質として使用した。マグネチックスターラーを使用して室温でフラスコの内容物を２４時間混合した。このようにして、スルホラン中のトリフルオロメタンスルホン酸リチウムの１Ｍ溶液中の、多硫化リチウムＬｉ２Ｓ６の０．２５Ｍ溶液を作製した。
(Preparation of electrolyte containing lithium polysulfide)
2 g of sublimed 99.5% sulfur (Fischer Scientific UK) and 0.57 g of 98% lithium sulfide (Sigma-Aldrich, UK), both in high speed mill (Microtron MB550) for 15-20 minutes And pulverized under a dry argon atmosphere (water content 20 to 25 ppm). The ground mixture of lithium sulfide and sulfur was placed in a flask and 50 ml of electrolyte was added to the flask. A 1M solution of lithium trifluoromethanesulfonate (available from 3M Corporation, St. Paul, Minn.) In sulfolane (99.8%, a GC reference material available from Sigma-Aldrich, UK) was used as the electrolyte. The contents of the flask were mixed for 24 hours at room temperature using a magnetic stirrer. In this way, a 0.25 M solution of lithium polysulfide Li 2 S 6 in a 1 M solution of lithium trifluoromethanesulfonate in sulfolane was prepared.
実施例１に記載されるようにして、実施例２による電解質を吸収させたＣｅｌｇａｒｄ ３５０１で分離した２つのリチウム電極を有する電気化学セルを作製した。 An electrochemical cell having two lithium electrodes separated by Celgard 3501 that absorbed the electrolyte according to Example 2 was prepared as described in Example 1.
ＭＣＶ １６−０．１−５電池テスター（Ｂｉｔｒｏｄｅ Ｃｏｒｐｏｒａｔｉｏｎ）上で０．２ｍＡ／ｃｍ２の電流負荷で上記セルのサイクルを行った。カソードおよびアノードの分極はそれぞれ１時間行った。このセルのサイクル中に得られたクロノポテンショグラムを図２に示す。 The cell was cycled with a current load of 0.2 mA / cm 2 on an MCV 16-0.1-5 battery tester (Vitrode Corporation). The cathode and anode were each polarized for 1 hour. The chronopotentiogram obtained during this cell cycle is shown in FIG.
図１および２を比較すると、電解質組成物中に多硫化リチウムを加えることで、リチウム電極のサイクル寿命が３倍を超えて増加することが示されている。 Comparison of FIGS. 1 and 2 shows that the addition of lithium polysulfide to the electrolyte composition increases the cycle life of the lithium electrode by more than three times.
本明細書の説明および特許請求の範囲の全体を通して、単語「含む」（ｃｏｍｐｒｉｓｅ）および「含有する」（ｃｏｎｔａｉｎ）およびこれらの単語の変形、例えば「含んでいる」（ｃｏｍｐｒｉｓｉｎｇ）および「含む」（ｃｏｍｐｒｉｓｅｓ）は、「含むが、それらに限定されるものではない」ことを意味し、他の部分、添加剤、成分、整数、およびステップを排除することを意図するものではなく排除するものではない。 Throughout the description and claims, the words “comprise” and “contain” and variations of these words, such as “comprising” and “including” ( "comprises" means "including but not limited to" and is not intended to exclude, but does not exclude other parts, additives, ingredients, integers, and steps. .
本明細書の説明および特許請求の範囲の全体を通して、文脈上で他の意味が必要となるのでなければ、単数形は複数形を包含している。特に、不定冠詞が使用される場合、文脈上で他の意味が必要となるのでなければ、本明細書は複数形および単数形を意図しているものと理解すべきである。 Throughout this description and the claims, the singular includes the plural unless the context requires otherwise. In particular, where indefinite articles are used, it should be understood that the specification is intended to be plural and singular unless the context requires otherwise.
本発明の特定の態様、実施形態、または実施例とともに記載されている特徴、整数、特性、化合物、化学的部分、または基は、それによって矛盾が生じるのでなければ、本明細書に記載の任意の他の態様、実施形態、または実施例に適用可能であることを理解されたい。 A feature, integer, property, compound, chemical moiety, or group described with a particular aspect, embodiment, or example of the invention, is not limited to any described herein unless otherwise contradicted. It should be understood that other aspects, embodiments, or examples are applicable.
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-
2006
- 2006-08-10 GB GBGB0615870.3A patent/GB0615870D0/en not_active Ceased
-
2007
- 2007-08-09 JP JP2009523355A patent/JP2010500709A/en not_active Withdrawn
- 2007-08-09 WO PCT/GB2007/050479 patent/WO2008017888A1/en active Application Filing
- 2007-08-09 CN CNA2007800296742A patent/CN101501897A/en active Pending
- 2007-08-09 GB GB0715423A patent/GB2440823B/en active Active
- 2007-08-09 EP EP07789366A patent/EP2050154A1/en not_active Withdrawn
- 2007-08-09 KR KR1020097002608A patent/KR20090037932A/en not_active Application Discontinuation
- 2007-08-10 US US11/889,334 patent/US20080038645A1/en not_active Abandoned
-
2010
- 2010-09-20 US US12/886,009 patent/US20110008683A1/en not_active Abandoned
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9203108B2 (en) | 2011-11-14 | 2015-12-01 | Samsung Sdi Co., Ltd. | Electrolyte for rechargeable lithium battery, and rechargeable lithium battery including the same |
| WO2013180522A1 (en) * | 2012-05-31 | 2013-12-05 | 주식회사 엘지화학 | Lithium secondary battery |
| US9287559B2 (en) | 2012-05-31 | 2016-03-15 | Lg Chem, Ltd. | Lithium secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2440823A (en) | 2008-02-13 |
| GB0715423D0 (en) | 2007-09-19 |
| US20110008683A1 (en) | 2011-01-13 |
| GB0615870D0 (en) | 2006-09-20 |
| CN101501897A (en) | 2009-08-05 |
| US20080038645A1 (en) | 2008-02-14 |
| GB2440823B (en) | 2009-09-16 |
| KR20090037932A (en) | 2009-04-16 |
| WO2008017888A1 (en) | 2008-02-14 |
| EP2050154A1 (en) | 2009-04-22 |
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